Module 5: Synthesis of nanomaterials: The Bottom-Up Approach

As we all aware, there are two important synthetic strategies for the generation of the
nanomaterials. They are two opposite approaches. The first one being top-down approach and
the second is bottom-up approach. This module is specifically intended to discuss various
bottom-up approaches. Here, nanomaterials are synthesized by assembling the
atoms/molecules together. The starting material is ether in gaseous or in liquid state. The
pictorial representation of the bottom-up approach is

Here, atoms are assembled together to get group of atoms or clusters. The clusters then
converted to nanoparticles or nanoscale materials. That is in the bottom-up approach, we begin
the synthetic strategy from atoms or molecules. Now let us move on to different the bottom-up
methods. The popular the bottom-up methods are:

❑ Chemical reduction
❑ Chemical Vapour Deposition (CVD)
❑ Sol-gel synthesis
❑ Hydrothermal synthesis
❑ Co-precipitation
❑ Spray pyrolysis
❑ Electrodeposition
❑ Molecular Beam Epitaxy
Let us discuss each and every method under this title.

Chemical reduction

Chemical methods are the common method of synthesis of nanoparticles. Colloidal Ag,
Au and Cu can be prepared by the reduction of their precursor salt solution. Reducing agents
like NaBH4 can be used under ice cold conditions to yield nanoparticles. Some illustrations of
the chemical reduction methods are shown here. For instance, Ag Nanoparticles can be
obtained by the reduction of AgNO3 solution using NaBH4 under cold conditions.

Nanoparticles of molybdenum can be obtained by the reduction of MoCl3 solution using

NaBEt3H (sodium triethyl borohydride)

MoCl3 + 3 NaBEt3H Mo + 3 NaCl + 3/2 H2 + 3 BEt3

The reduction in the presence of a capping agent like citrate yields capped nanoparticles. Au
NPs are produced by reduction of the chloroauric acid (HAuCl4). HAuCl4 is converted into
Au NPs by using ascorbic acid as reducing agent ad citrate as capping agent

Chemical Vapour Deposition (CVD)

What is happening during chemical vapour deposition? CVD is a method to produce
high purity high performance solid-materials. It involves the formation of the nanomaterials
from the gas phase at elevated temperatures- usually on to a substrate or catalyst. In CVD, a
thin film is formed on the substrate surface via the chemical reaction of vapor-phase precursors.
A precursor is considered suitable for CVD if it has adequate volatility, high chemical purity,
good stability during evaporation.
CVD precursor materials fall into a number of categories such as:
➢ Halides - TiCl4, TaCl5, WF6, etc.
➢ Hydrides - SiH4, GeH4, NH3, etc.
➢ Metal Carbonyls - Ni(CO)4, etc.
➢ Metal Organic Compounds

There are several types of CVD. This is because CVD is CVD is practiced in a variety
of formats. These processes generally differ in the means by which chemical reactions are
initiated
Some important types of CVD are:
➢ Atmospheric Pressure Chemical Vapour Deposition (APCVD)
➢ Low Pressure Chemical Vapour Deposition (LPCVD)
 ➢ Metal-Organic Chemical Vapour Deposition (MOCVD)
➢ Laser Chemical Vapour Deposition (LCVD)
➢ Plasma Enhanced Chemical Vapour Deposition (PECVD)

In CVD, During the process, the substrate (wafer) is exposed to one or more volatile
precursors which react and decompose on the substrate. Laser beam or plasma can be used to
enhance the reaction. Volatile by-products obtained during the process are removed by gas
flow through the chamber. The pictorial representation of the CVD is

Sol-Gel Synthesis
The sol–gel method is a wet-chemical technique that is extensively used for the
development of nanomaterials. It is the production of the solid materials like metallic oxides
from the solution state reactants or precursors. This method is used for the development of
various kinds of high-quality metal-oxide-based nanomaterials. A sol is a colloidal or
molecular suspension of solid particles or ions in a solvent. A gel is a semi rigid mass that
forms when the solvent from the sol begins to evaporate and the particles left behind begin to
join together in a network. Sol-gel process is a wet-chemical synthesis.

The process generally begins with mixing of precursors in a suitable solvent. The sol-gel
process proceeds through the following steps:

➢ Formation of stable solutions of the precursor

➢ Hydrolysis
➢ Condensation
➢ Gelation
➢ Aging
➢ Drying and densification
We can move on to the details of each and every steps.

1. Formation of stable solutions of the precursor

➢ Precursors are the starting materials and the common precursors are the metal
alkoxides or chlorides
➢ It is dissolved in a solvent to get a stable solution

2. Hydrolysis

➢ During hydrolysis, the alkoxy group(-OR) of precursor is replaced by hydroxyl (-OH)

group of water

MOR + H2O → MOH + ROH

3. Condensation

➢ The condensation can be generally represented as

MOH + XOM → MOM + XOH

Here, M is a metal; and X is H or R (alkyl group)

4. Gelation

➢ Gelation is the process by which the sol undergoes transition from liquid solution to a
crosslinked gel

➢ Viscosity of solution increases rapidly during gelation

5. Aging

➢ After gelation, the next step is aging during aging, the structure as well as the
properties of the gel network continuously changes till the target density is achieved

6. Drying and densification

➢ Drying is the solvent evaporation from the medium

➢ During densification the product mixture attain desired density

Advantages of Sol-gel synthesis

The advantages of sol-gel synthesis are:

1. Smaller particle size

 2. Better control over morphology of the particles
3. Highly suitable for thin film deposition
4. It can produce high purity nanomaterials
5. It can be used to produce powders and fibers

Hydrothermal synthesis

It is one of the most well-known and extensively used method to produce

nanostructured materials. Here, nanomaterials are obtained through a heterogeneous reaction
carried out in an aqueous medium at high pressure and temperature in a sealed vessel. Process
is at a high vapor pressure level and using a high-temperature aqueous solution. Hence it is
termed as ‘Hydro’ + ‘Thermal’ = Hydrothermal method.

Hydrothermal synthesis - Instrumentation

Since hydrothermal synthesis involves high temperatures and pressures, the reaction
container must be able to sustain such conditions. Hence, Hydrothermal synthesis needs a
special device called Hydrothermal Autoclave. The reactants are dissolved in water or another
solvent(solvothermal) in autoclave and heated above b.p. This is the pictorial representation of
autoclave.

Solid reagents can be mixed with water in the autoclave and covered it with lid. This
instrument can be heated up to desired temperature, to perform the hydrothermal synthesis.

Hydrothermal synthesis -Advantages

It is useful for producing various nano-geometries such as nanowires, nanorods,

nanosheets, and nanospheres. It gives good control over the particle shape and size. It can also
be used for producing large and high purity crystals having well controlled compositions.
Co-precipitation

Here, the required metal cations, taken as soluble salts are co-precipitated from a
common medium, usually as hydroxides, carbonates, oxalates or citrates. The precipitate
obtained after drying is heated to the required temperature in appropriate atmosphere to
produce the final product. It is a very simple method for the synthesis of nano powders. For
instance, iron oxide nanoparticles can be prepared by this method

Fe2+ + 2Fe3+ + 8OH- → Fe3O4 + 4H2O

One of the drawbacks is the difficulty of controlling the particle size and morphology

Spray Pyrolysis

Spray pyrolysis is a process in which a precursor solution is atomized, evaporated and

then decomposed into particles and film. Spray pyrolysis includes spraying of the metal salt
solution on a preheated substrate. Drops sprayed onto the substrate, stretch as disks and are
thermally decomposed.

A standard spray pyrolysis instrument includes:

➢ An atomizer
➢ The precursor solution
➢ A substrate heater and
➢ A temperature controller

A schematic diagram of spray pyrolysis

Temperature and precursor solution affect the structure and properties of films deposited via
spray pyrolysis.
Electrodeposition

It involves formation of a metallic coating onto a base material (substrate) through the
electrochemical reduction of metal ions from an electrolyte. This bottom-up approach is
versatile and can be applied for depositing nanostructured thin films. Electrodeposition of
metallic layers from aqueous solution is based on discharge of metal ions at a cathode surface
(substrate). The metal ions accept electrons from the electrically conducting material at the
solid-electrolyte interface and then deposit. The electrons required for this process are either
supplied from an externally applied potential source or from reducing agent present in solution
(electroless reduction). Electroplating is another technique analogous to the electrodeposition.

Factors Influencing Electrodeposition

The factors are:

➢ Current density
➢ The nature of the anions and cations present in the solution
➢ Composition as well as the temperature of the bath
➢ Concentration of the solution
➢ The presence of impurities
➢ Physical as well as chemical nature of the surface of the substrate

Molecular Beam Epitaxy (MBE)

The term epitaxy originates from the Greek roots “epi” and “taxis” which mean to
arrange upon. Molecular beam epitaxy (MBE) is an epitaxial growth technique used to deposit
thin-film of single crystals. MBE involves taking a base material called substrate, onto which
the film will be deposited. The substrate can be a semiconductor like silicon (Si), germanium
(Ge), or gallium arsenide (GaAs). The substrate is heated up to a suitable temperature. The
precursor material is heated to high temperatures such that it is present in gas state. The gaseous
precursor is then bombarded on to the substrate in the form of focused beam of atoms or
molecules.

The atoms or molecules, on reaching the surface of the substrate condense and
gradually grow into ultra-thin layers.
MBE-Advantages

Advantages includes the following:

➢ It can be used to prepare high quality, defect-free, and highly uniform semiconductor
crystals of a wide array of compound
➢ Precise control over film thickness is possible

Bottom-Up Approach: Advantages

➢ Ultrafine nanoparticles can be prepared

➢ Narrow size distribution is possible (1-20 nm)
➢ Cost effective procedure

Bottom-Up Approach: Disadvantages

➢ Large scale production is difficult

➢ Chemical purification of nanoparticles is required

Now it is possible to conclude, the entire synthetic approaches. By the last two discussion,
we have covered the top-down and bottom-up approach for the synthesis. These two
approaches have several advantages and disadvantages. The picture is a consolidation of both
approaches together.